Naphtho-carbazole-hydroxy-azo dyestuffs



Patented June 24,1930

UNITED STATES HARRY GnIMMnL, or WIESDORF-ONJTHE-BHINE, AND, HEINRICH oLINGEsrEIn, or

GOLOGNE-ON-THE-RHINE,

GERMANY, ASSIGNOBS To GENERAL ANIL'INE WOBKS,1

me, or new YORK,'I\T.' YQA coarona'rron' or DELAWARE llTAIHTHO-CARIBAZOLE-HYDROXY-AZO DYESTUFFS i No Drawing; Application filed June 28, 1926, Serial No. 119,196, and in Germany June 26, 19251;.

The present "invention relates to new azo dystufis, and more particularly relates to azo dyestuiis which are obtainable by coupling an unsulfonated diazo compound with an unsulfonated I hydroxy naphtho carbazolecompound which may be substituted by an alkyl group or by halogen.- 1

We haveyfound that the aforesaid hydroxynaphtho-carbazole compounds couple easily with unsulfonated diazo compounds and lend themselves excellently to the production of azo dyestufis which are distinguished by very good fastness properties. j.

- The hydroxy-naphtho carbazoles them- 5 selves are best prepared by condensinghydrazines with naphthol or naphthylamine' sulfonic acids in the presence of alkali metal bisulfite (see Bucherer, Journal fiir praktische chemie, Vol. 81, 1910, pages 22 and fol- 2 lowing) and replacing the sulfo group by the hydroxy group'by means of an alkali .melt;

i The 2-1-naphtho-carbazoles of theformula:

formula as well as the 1-2-naphtho-carbazoles of the i lene as the benzene nucleus are useful for the" production of our novel azo dyestiifisigj},

These novel dyestufls can be'prlhduced in substance or on the fibre, and by varying the diazo compound, all possible shadescan be obtained, the dyestuiis repared on "the fibre being particularly use ul. The fibre material is then padded with the hydroxy-naphtho-carbazole and developed by passing through a :bath of the desired-.dia'zo compound. .The dyeings so obtained are parto boiling, chlorine, light, ki'er ticularly vfast boiling, etc.

The two radicle -enters by this -reaction into the naphthalene nucleus of the naphtho-carbazole 'and,"by reducing the dyestufi, an arcmatic amineis recovered together with an amino-hydroxy-naphtho carbazole, in which both the amino and hydroxyl groups are attached to the naphthalene nucleus.

Our invention is further-illustrated the following examples, the parts being byweight, but it is understood that our invention is iiot'limited to the particular substances nonreacting conditions described therein.

Emample 1 .-13.8 parts of m-nitro aniline are .diazotized in the usual manner and the resultingdiazo solution run. into a soda alkalinev solution of 23.5 parts of 7-hydroxy-2-1- naphthp-carbazole, of theformula 11 which, by addition of sodium carbonate, is. kept, alkaline. The dyestufi' quickly forms and separates. It is isolated in the usual way.

7 It i's when fdry, a reddish-brown powder, practically insoluble in water. but soluble in concentrate sulfuric acid with a red color.

By reduction, as for example with tinchloride and hydrochloric acid, m-phenylene diamine and 8amino-7-hydroxy-2-l-naphthocarbazole are obtained. The dyestufi' has 6 mostprobablythe formula:

l [t can be produced on the fibre in the.followmg manner:

5 parts of 7 -hydroXy-2-1-naphtho-carbazole .are'brought to a paste, in the cold,

Y with 7.5 parts of Turkey-red oil and from 7.5 to 10 parts of 34 B. caustic soda, andthe resulting paste is then disolved in 500 parts of boiling water; this solution is brought to about 1000 partsby the addition of 500 parts of cold water, and 5 parts of'40% formaldehyde solution are added. Cotton goods are then padded withthis solution and, after.

eventual drying, developed with a solution of m-diazo-nitrobenzene; The cotton goods are 'dyed a reddish-brown ofexcelle nt fastness to boiling, light, chlorine and kier boil- %xample 2.- Gotton material is padded with a soda alkaline solution of 7-hydroXy-2- and developed with a solution of 4-nitro-1- methoxy-Q-diazmbenzene. The material is ing, light, chlorine and kier boiling.

0 Example 4. Cotton' material is padded and light.

.with a solution of 'Z-hydroxy-Q-l-naphtho-5'- methyl-carbazole of the formula:

tained from l-nitro-2-toluidine a beautiful claret shade of good fastness to boiling,

chlorine, light and kier boiling, is obtained.

Example 5 .Hydroxy-naphtho-carbazoles can also be usedin calico printing. The following is an exemplification of such a pro-- cedure. The goods are padded with a solution containing in 10 liters 240 grams of 7'- hydrOxy-Q-l-naphtho-carbazole, 300 grams of Turkey-red oil and 380 grams of 36 Be/caustic soda. After drying they are printed with a printing paste containing thickening, aluminum sulfate. and the diazo compound obtained from p-nitro-o-anisidine. The goods are then dried, washed, soaped and finished. They are printed a brownish-black of very good fastness to chlorine, washing Example 6.15.2 parts of 4-nitro-2-to1uidine are diazotized in the usual manner and the resulting diazo solution is run into a soda alkaline solution of 23.5 parts of 7-hydroxyl-2-naphtho-carbazole, kept alkaline by the addition of sodium carbonate. The dyestufi? separates and is'isolated in the usual way.

It is, when dry, a brownish-red p owder,'s0luble in concentrated sulfuric acid With-a red- V dish-violet color. It yields, on reduction with tin chloride and hydrochloric acid, 2-4- itoluylene diamine and 8-amino-7-hydroxy-1- Q-naphtho-carbazole.

Example 7.By combining, in a similar manner, the diazo compound obtained from l-nitro-2-toludine with 5-hydroXy-2-1-naphtho-carbazole a dyestulf of the probable formula OH 4 N03 H: is obtained.

It is a brown powder soluble in concentrat- 125 I ed sulfuric acid with bluish-violet color.

It yields, on reduction with tin chloride and dyed a violet-black of good fastness to boilhydrochloric acid, 2-4-toluylene diamine and 6-amino-5-hydroXy-2-1-naphtho-carbazole.

Example 8.By combining, in a similar manner, the diazo compound from 4-ni'tro-2- toluidine with 6-hydroxy-2-1-naphtho-carbazole a dyestuff of the probable formula:

is obtained. It is in the dry state a brown powder, soluble in concentrated sulfuric acid wherein R represents an unsulfonated aryl compound ofthe/benzene series.

3. a new the formula:

whioh dyestufi is, in dry form, a reddishbrown powder soluble in concentrated sul-.

furic acid with'a redcolor. v I

4. Cotton material dyed with the azo product the azo dyestufl of sulfonated hydroxy-naplitho-carbazole cornpound which may be substituted by an'alkyl group or halogen with an unsulfonated diazo compound of the benzene series containing" a nitro group.

5. Cotton material dyed with the azo dyestuffs of the general formula;

wherein R represents an unsulfonated aryl compound of the benzene series. 6. Cottonmat'erial dyed with stuff of the general formula which dyestufl is, in dry form, a reddishbrown powder soluble in concentrated sulfuric acid with a red color.

. In testimony whereofwe have hereunto set our hands. HARRY GRIMMEL. HEINRICH CLINGESTEIN.

dyestuffs obtainable by coupling an run- A the azo dye- 

